Oxidation of ammonia



,'Feb. l1, 1941.

v. M'. sTowE i OXIDATION OF AMMONIA Filed June 28, 1958 I MSS swh

' y BY' i C, ATTORNEY S EN@ "'35 of cob f f vet-toom. stowepreterebo'rafve.;mignot-itol t s1 .TheSolvayProcesc Company-,rhein Yorkgmye ...y @.wrporationiotNewYoi-k j` 1 31' l'miuettioiiy gs, 19st. Serin No. 21ans ilacieime.. (ci.trs-1cm#4 This"l invention relatesrjf to processes for 'the manufacture;1` of catalystad More `particularly vating spent cobalt oxide Acatalysts"used "in 5 `theoxidationfof ammonia. l if yUnited states vPotent'trio.11.952,91; issued; to De Rewoi oiiA iinereiizfz.A 1934,` necios'espt.` procese -for reactivating cobalt ioxiden'catalysts. involving digesting "ther eetaiystgwith; hydrochloric acid,

` l separatingfthe :catalys'tfmaterialfirom the.acid.

#wetting itwitii iiitrieaidfand uniting.; `Futthermor'e, United States Patent No. 2,017,683318- sued to Crittenden onOctoberl, `19.35 describes a. process for preparing'fhighly" active` cobalt oxide i l catalysts jforf the oxidation'` of ammonia from cobalt oxide 01:'y low catalytic Jactivity or 'Qfroxn cobalt oxidejcatalyst which Ahas become. spent `through prolonged in' .the oiddation'pfammoniay'which involves' reducing the` oxide to t cobalt metalffwithcarbofn in an electricurnaoe,

treating the cobalt `motel thus obteinediwitn a iiux,` 'separating the `fused` metal from L the `sialg which forms,` and thentoonverting the thustreat-V i ed cobalt metal to cobalt `oxide catalyst. While u this ietterprooesefprodoeee highiyjeotive cobalt mdsseilysts .mathe when or, emmene. e crtanjamolmt ofthe metal maybe st' 11131I1g'0peration-l so "simple andfsonmiceizmethvd for' stepwise cobalt oxide "'c iattalysts` (for the oxidation of i ami .14o oxide catalysts ftheeeteiytio eetivityoffwicn has been decreasedbyuse fortheoxidationof ammonia andrfrom other gradesvof cobalt oxide of lowl catalytic activity, e. 'g`. commercial cobalt oxide, by reducing. the` oxide `.to t cobalt i `metal with a hydrogencontaining gas and converting the cobalt `metal thus' obtained to cobalt oxide. iIihave also i'ound thatwthefreductlon ofcobalt .oxide by passing `aihydrogen-containing` gas thereover'produces acobalt-metal which is highfly `reactive and especiallyrsuitable yfor' `dissolving in nitric: acid.y Due` tolits I reactivity, it nitty be dissolved f inl nitric acid'withoutthefuse oiffttn` exthis inventionrelates-1to aprocess forfthefreacdisc ery 'jthah Q'. l, f t M y 4 winLaccordancewith'thisjinventionl proceedsl a1- '.niost dibaticlly et t, tempratures between. about, gqandabout 500` C.r It is thereforefde- 40 fsirableto yprfeheejtt`.v the hydrog'en'containing .gas [before ,passing it over fthe, cobalt'y `oxide to` tem- Peratures iwithlnthis for underesuh wn- `t'itios,"providing the enclosure in which the rei auction is earned outr is prcperlyfinsulated, Athe 4s Vreduetiifmmay be eiected `withoutsupplyirig any "additional `heat tothe oxide. The "rate` of ow f jofgasthroiigh the "reduction chamber mayvary ysolution andfcan-befflltered ofrvvherebythevproduction ofacatalyst of high activity iseffected.

In accordance with Athe process `of 4this i invent tion.` cobaltiotide, preferablyjingranular form..

is reduced; by passing hydrogen-containing gases 5 'thereoven .The cobalt .oxide which is Vto tbe treated according tothis intention may contain @particles of undesirable. nenesswhich` impede p the ow 'of the hydrogen-containing, gas `,through the oxide These Lfines are. therefore, relo moved from the remaining oxide Lmatex'ialtby screening.r granulated by ignition with aurelaftivelysmall. amount ofcobalt nitrate,.and the "granules addedto the oxide massbeing treated. .The hydrogenecsntsmins .ees may` ,be -substen- 1 ,tially'pure *hydrogen or any hydrogen-,containing gas( containing above.. approximately, 10% Ahydrogierh4 eifgga`gas con-tainingdfz? hydrogen, and having no substances therein which wouldpoison or otherwisedetrimentally aifectethe catalytic 20, i Yactivity of` thel :product of this, invention. En l, where'. `preparatim. of Athe catalyst is vcarried out i in `conjunction with the synthesiso! ammonia,v `a. hydrogen-containing gas eminently l. adapted ioi" .the purposes oi! this ii'ivention is` 25 v`available.in (largelquantities. 'in theioxfm of the. f bleevler;A eas "witidrawn trom the 2111111110111?. synflltlesls system. i This sas containsabout. hy-

drogen and containsno substanceswhich would,

oncontact .with :the cobalt `OXilebeing treated. '30 n tendv to poison "or t otherwise tdetrlmentally `afjfeet the catalyst.` produced `by the process of this invention: "Whenever the term '.i'bleeder gas..1s pusedin thespecication and claixnsdt is 'to ,be `Iunderstood.,ioleedercesfrom ammonio. synthesis 35 `Lis referred to.'

'Ithasbeen fouiio the reduetion'ofpeobait oxide considerablybut whenusing lbleeder gais alrate ,f

of u'novit of valcz'nit 1000 Evolumes oi'gas per volume' '50 f ofy catalyst "per hour 4has ybeen found .suitable. i'I'iieI-tiroeneeessayljto eneet substantially oom- "pleter'eduction of the cobalt oxide willl` vof course, vary "depending" upon i the h:sidxf'ogertv content of "tl'i'gas d thrate'lf OW thereon' however.

when c arrying out the reduction according to the preferred embodiment of this invention, i. e. when bleeder gas is passed over the cobalt oxide at a rate of about 1000 volumes per part of cobalt oxide per hour, it has been found substantially complete reduction of the cobalt oxide may be effected irl-about an hour.

The reduction of cobalt oxide as above described produces cobalt metal; it has been found the metal thusy produced is in a'pyrophoric condition so that it is necessary to submerge it in water during storage or handling. The cobalt metal may be converted to cobalt oxide catalyst in any suitable manner.- Since the cobalt metal Aproduced by the process of this invention is in.V

such a form that it is readily solublein nitric acid, preferably the metal is convertedto the oxide by dissolving the metal in nitric acid,

evaporating the solution to. recovery' cobalt xiitrate therefrom, and igniting the nitrate to produce cobalt oxide. v `As above indicated, lI have found the solution'of the cobalt metal produced vv'in accordance with this invention may be effected without'using a substantial excess 0f the acid vover vthat necessary to combine with the cobalt so'th'at asubstantially neutral solution of cobalt nitrate may' be formed; this is particularly advantageous not only because it resultsin a saving of' acid butalso because ink such neutralsolutionsany impurities such as iron and phosphorus present in the cobalt metal, the

o presence of .which in the catalyst product tends to'impair its* eiiiciency form insoluble precipiv`tates,le. g.- iron oxide or hydroxide, iron phosphate, etc., and thus these impurities may be removed byr al simple filtration. Furthermore, any cobalt oxide which remains unreduced or which has been accidentally re-oxidized may be A 'removedfrom the substantially neutral solution 'formed and returned to the reduction step of the process of this invention. The reduction f cohalt oxide in accordance with this invention when followed by the above method ofdissolving "the 'cobalt metal effects the. production from of a catalyst containing practically no impurieither-crude commercial cobalt oxide'orfrom spent cobalt oxide ammonia oxidation catalysts t ties andfhaving a higher degree of porosity and [a higher'catalytic activity than catalysts 'duced by'y other methods.

In the accompanying drawing forming apart of this specification and showing for purposes ofl `exempliiication a preferred form of apparatus in which this invention may becarried out, bleeder gas is withdrawn'froml the ammonia. synthesis system, passed through high pressure vgas expansion valve I and then through ilow'meter 2 .to-preheater 3 through valve l. Relief valve 5 is also provided in the line. Preheater burner `B' supplies heat to preheater 3. The fuel for preheaterburner 6l may be obtained bytapping the bleeder gas line at 1 and withdrawing a portion ofthe bleeder rgas through valve 8`to burner V6; or thefuel may be vsupplied from the exit gases fromy reduction furnace 8, as hereinafter described. In preheater 3 the bleeder gas is heatyed to a temperature between about 320.and 3 about`500"vr C. It is then passed into lreduction furnace 9, which ispreferably heat insulated, wherein the cobalt oxide in granularjform is disposed. The gas, after passage over the cobalt oxide, 4 is removed lfrom reduction lfurnacelluat I0v and may be vented through valve, il or passed to preheater burner 6, throughrvalvle I2,

as above described. When'lreduction is cni-l plete, steam is passed into reduction furnace 8 to cool the reduced metal, after which water is passed into furnace 9 to submerge the cooled metal, which, as above pointed out, is pyrophoric.

The following examples are illustrative of this invention. Amounts are given in parts by weight. The oxidation emcienci' mentioned in the examples represent the eiciency of the parfticularcatalyst in converting a. mixtureof air and ammonia containing 8.7% ammonia to nitrogen oxides at a temperature of '780 C., and a pressure of one atmosphere, the gas being passed over the catalyst at a. .space velocity of 45,000.

"Example 1.'-460 parts of cobalt oxide, the catalytic activity of which had been decreased by use '.for the koxidation of ammonia, were brought to a temperature of 350 C. Bleeder `gas at approximately the same temperature and containing 65% hydrogen was then passed over the heated cobalt oxide at a rate of about 250 liters per hour. At the-'end of one hour it was found that substantially all the cobalt oxide-had been reduced to cobalt metal.v 'I'he metal thus obtained was dissolved in about 1,500 ,parts of 68% nitric acid, the solution evaporated .to ob- Utain cobalt nitrate crystals, and the nitrate crystals ignitedat 500 C. to produce cobalt oxide.' By this process approximately 440 parts of cobalt oxide were obtained, the oxidation efficlency of a screened portion of which was 97% as compared to thatv of spent catalyst granules of substantially the same size, which was only 91.8%.

Example 2.-'460 parts of cobalt oxide.' the catalytic activity of which had been decreased by use for the oxidation of ammonia, were reduced in themanner described in Example 1, dissolved ln about 1,360 parts of 68% nitric acid, and the solution evaporated. The cobalt nitrate was recovered in two lots; one lot being obtained by fractionaliy crystallizing approximately 50% of the cobalt nitrate from the' solution, and the other being obtained. by evaporation of thel mother liquor. Both these samples were ignited at 500 C. to form cobalt oxide catalyst.

In the following table,rSamples. 1 and 2 are 'cobalt'. oxide catalystsiprepared in accordance 'With Example 2, Sample 1 being Obtained from ignition of cobalt nitrate crystals recovered by Vfractional crystallization, and Sample 2 being obtained by evaporationv and ignition of. the mother liquor.r Sample3 is a l'cobalt oxide catalyst reactivated byheating 230 parts of the same spent catalyst as used in Example 2 with 200 parts of 5% hydrochloric acid, separating thel acid and catalyst by decantation, washing the catalystwith water,kwetting it with 60 parts of 68% nitric acid, heating to evaporate the acid,

It is obvious from the above table that cobalt -oxide catalysts having high oxidation eiilciencies may be prepared in accordance with my invention from spent cobalt oxide ammonia oxidation catalysts of relativelylow emciency. yFurthermore, the'I-oxidation emciencies of catalysts pre-v 1l i pared by the process ci' my invention are dis tinctly higher than those of catalysts reactivated by treatment with hydrochloric and nitric acids as described. It is also apparent that catalysts reactivated in accordance with this invention have a higher degree of porosity, i. e., have a lower apparent density than catalysts react vated by other processes.

While the above examples describethe process of my invention as applied to the preparation of highly active cobalt oxide catalysts from cobalt oxide catalysts, the catalytic activity of which has been decreased by use for the oxidation of ammonia, it will be understood these examples are for the purposes of illustration only and that my invention is also applicable to the preparation of highly active cobalt oxide cata# lysts from other grades of cobalt oxide of low catalytic activity, e. g., commercial cobalt oxide.

By the process of this invention it is possible to obtain highly active cobalt oxide catalysts for the oxidation of ammonia in a. simple and economical manner. Losses of metal are almost entirely avoided and impurities in the cobalt -oxide starting material may be readily removed.

This process is therefore extremely useful in theV manufacture of ycobalt oxide catalysts for the oxidation of ammonia.

l. A process for the production ci' cobalt oxide catalysts which comprises reducing cobalt oxide to cobalt metal with a hydrogen-containing gas at a temperature in the rangeoi about 320 to 500 C. and thereafter converting the cobalt metal substantially completely to cobalt oxide.

2. A process for regenerating spent cobalt oxide `catalysts ior 4the oxidation of ammonia which comprises reducing the spent cobalt oxide to cohalt metal by passing a hydrogemcontaining gas `thereover at a temperature in the range of about 320 to 500 C. and converting .the cobalt metal thus obtained substantially completelyto cobalt oxide. 3. A process for the production of cobalt oxide catalysts for the oxidation of ammonia which in the range of about 320 to 500 C. and converting .the cobalt metal substantially completely to cobalt oxide.

5. A process for producing cobalt oxide catalysts for lthe oxidation of ammonia from cobalt oxide catalysts, the catalytic activi-ty of which has been decreased by use for oxidation of ammonia, which comprises reducing the spent cobalt oxide to cobalt metal with bleeder gas at a temperature in the range of about 320 to .500 C. and converting the cobalt metal substantially completely to cobalt oxide.

6. A process for producing cobalt oxide catalysts which comprises reducing cobalt oxide to cobalt metal with a hydrogen-containing gas at a temperature in the range of about 320 to 500 C.. dissolving the cobalt metal substantially completely in nitric acid, and evaporating and igniting th solution of cobalt nitrate to produce cobalt oxide.

'7. A process for the production of cobalt oxide catalysts of high activity for the oxidation of ammonia from cobalt oxide catalysts, the catalytic activity of which has been decreased by use for the oxidation oi ammonia, rwhich comprises screening the spent cobalt oxide .to remove cobalt oxide nes, granulatingthe fines by ignition with a relatively small amount of cobalt nitrate, mixwhich comprises contacting a gas containing ammonia and oxygen with a catalyst prepared by reducing cobalt oxide to cobalt meta-l by 'means of a hydrogen-containing gas ata .temperature in the range o1 about 320 to 500 C. and converting .the cobalt metal thus obtained substantially completely to cobalt oxide.

9. A process for the oxidation of ammonia which comprises contacting a gas containing ammonia and oxygen with a catalyst prepared by reducing a cobalt oxide catalyst, the catalytic activity of which has been decreased by use for the oxidation o! ammonia, with bleeder gas at a temperature in the range of about 320 to 500 C. and

i converting the cobalt metal thus obtained substantially completely to cobalt oxide.

VERNON M. STOWE. 

